Preparation of catalyst systems

ABSTRACT

The present invention relates to a process for preparing a catalyst for olefin polymerization which is obtainable by bringing
     A) at least one organic transition metal compound,   B) a mixture of at least two different organo metallic compounds and   C) at least one cation-forming compound
 
into contact with one another, wherein the organic transition metal compound A) is firstly brought into contact with the mixture of the organo metallic compounds B). In addition, the invention relates to the use of the catalyst for olefin polymerization, to catalysts obtainable by this process and to a process for the polymerization of olefins in which these catalysts are used.

RELATED APPLICATION

This application is a national stage application (under 35 U.S.C. 371)of PCT/EP2003/007567 filed Jul. 14, 2003, which claims benefit to Germanapplication Serial Number 102 32 083.7 filed Jul. 15, 2002 and U.S.Provisional application Ser. No. 60/401,206 filed Aug. 5, 2002.

The present invention relates to a process for preparing a catalyst forolefin polymerization which is obtainable by bringing at least oneorganic transition metal compound, a mixture of at least two differentorganometallic compounds and at least one cation-forming compound intocontact wit one another, to the use of the catalyst for olefinpolymerization, to catalysts obtainable by this process and to a processfor the polymerization of oletins in which these catalysts are used.

Organic transition metal compounds such as metallocene complexes are ofgreat interest as catalysts for olefin polymerization since they make itpossible to synthesize polyolefins which cannot be obtained usingconventional Ziegler-Natta catalysts. For example, such single sitecatalysts lead to polymers having a narrow molar mass distribution and auniform comonomer content.

For organic transition metal compounds such as metallocene complexes tobe active as catalysts for olefin polymerization it is necessary forthem to be reacted with further compounds which serve as cocatalysts.One frequently used class of cocatalysts consists of aluminoxanes suchas methylaluminoxane (MAO). Further compounds which can be used ascocatalysts are compounds which convert the organic transition metalcompounds into cationic complexes.

In the preparation of olefin polymerization catalysts based on organictransition metal compounds, the organic transition metal compounds arefrequently reacted with an organometallic compound such as an aluminumalkyl before they are brought into contact with the further componentsof the catalyst, e.g. cocatalysts or supports. Particularly in the caseof sparingly soluble organic transition metal compounds, it has beenfound that a series of problems such as deposit fonnation in the reactoror an unsatisfact ry catalyst activity can occur.

It is an object of the present invention to find a process for preparingcatalysts for olefin polymerization which is relatively simple and leadsto catalysts having an increased polymerization activity or requires areduced amount of expensive starting materials such as boron-containingcompounds or transition metal compounds for the same polymerizationactivity. At the same time, polymerization without formation of depositsin the reactor should be possible.

We have found that this object is achieved by a process for preparing acatalyst for olefin polymerization which is obtainable by bringing

-   A) at least one organic transition metal compound,-   B) a mixture of at least two different organo metallic compounds and-   C) at least one cation-forming compound    into contact with one another, wherein the organic transition metal    compound A) is firstly brought into contact with the mixture of the    organo metallic compounds B).

Furthermore, we have found the use of the catalyst for olefinpolymerization, catalysts obtainable by this process and a process forthe polymerization of olefins in which these catalysts are used.

The catalysts prepared according to the present invention are suitablefor the polymerization of olefins and especially for the polymerizationof α-olefins, i.e. hydrocarbons having terminal double bonds. Suitablemonomers include functionalized olefinically unsaturated compounds suchas ester or amide derivatives of acrylic or methacrylic acid, forexample acrylates, methacrylates or acrylonitrile. Preference is givento nonpolar olefinic compounds, including aryl-substituted α-olefins.Particularly preferred α-olefins are linear or branchedC₂-C₁₂-1-alkenes, in particular linear C₂-C₁₀-1-alkenes such asethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene or branched C₂-C₁₀-1-alkenes such as 4-methyl-1-pentene,conjugated and nonconjugated dienes such as 1,3-butadiene, 1,4-hexadieneor 1,7-octadiene or vinylaromatic compounds such as styrene orsubstituted styrene. It is also possible to polymerize mixtures ofvarious α-olefins.

Suitable olefins also include ones in which the double bond is part of acyclic structure which may comprise one or more ring systems. Examplesof such olefins are cyclopentene, norbornene, tetracyclododecene andmethylnorbomene and dienes such as 5-ethylidene-2-norbornene,norbornadiene and ethylnorbomadiene.

It is also possible to polymerize mixtures of two or more olefins.

The catalysts of the present invention are particularly useful for thepolymerization or copolymerization of ethylene or propylene. Ascomonomers in ethylene polymerization, preference is given to usingC₃-C₈-α-olefins, in particular 1-butene, 1-pentene, 1-hexene and/or1-octene. Preferred comonomers in propylene polymerization are ethyleneand/or 1-butene.

As organic transition metal compound A), it is in principle possible touse any compounds of the transition metals of groups 3 to 12 of thePeriodic Table or the lanthanides which contain organic groups andpreferably form active olefin polymerization catalysts after reactionwith the components B) and C). These are usually compounds in which atleast one monodentate or polydentate ligand is bound to the central atomvia sigma or pi bonds. Possible ligands include ones containingcyclopentadienyl radicals and also ones which are free ofcyclopentadienyl radicals. A large number of such-compounds A) suitablefor olefin polymerization are described in Chem. Rev. 2000, Vol. 100,No. 4. Furthermore, polycyclic cyclopentadienyl complexes are alsosuitable for olefin polymerization.

Particularly useful organic transition metal compounds A) are onescontaining at least one cyclopentadienyl-type ligand. Those containingtwo cyclopentadienyl-type ligands are commonly referred to asmetallocene complexes. Among organic transition metal compounds A)containing at least one cyclopentadienyl-type ligand, compounds whichhave been found to be particularly suitable are those of the formula (I)

where the substituents and indices have the following meanings:

-   M^(1A) is titanium, zirconium, hafnium, vanadium, niobium, tantalum,    chromium, molybdenum or tungsten, or en element of group 3 of the    Periodic Table and the lanthanides,-   X^(A) are identical or different and are each, independently of one    another, fluorine, chlorine, bromine, iodine, hydrogen,    C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₆-C₁₅-aryl, C₇-C₄₀-alkylaryl,    C₇-C₄₀-arylalkyl, —OR^(6A) or —NR^(6A)R^(7A) or two radicals X^(A)    are joined to one another and together form, for example, a    substituted or unsubstituted diene ligand, in particular a 1,3-diene    ligand, or a biaryloxy group, where-   R^(6A) and R^(7A) are each C₁-C₁₀-alkyl, C₆-C₁₅-aryl,    C₇-C₄₀-arylalkyl, C₇-C₄₀alkylaryl, fluoroalkyl or fluoroaryl each    having from 1 to 16 carbon atoms in the alkyl radical and from 6 to    21 carbon atoms in the aryl radical,-   n^(A) is 1, 2 or 3, where n^(A) is such that the metallocene complex    of the formula (I) is uncharged for the given valence of M,-   R^(1A) to R^(5A) are each, independently of one another, hydrogen,    C₁-C₂₂-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may    in turn bear C₁-C₁₀-alkyl groups as substituents, C₂-C₂₂-alkenyl,    C₆-C₂₂-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, —NR^(8A) ₂,    —N(SiR^(8A) ₃)₂, —OR^(8A), —OSiR^(8A) ₃, —SiR^(8A) ₃, where the    radicals R^(1A) to R^(5A) may also be substituted by halogen or two    radicals R^(1A) to R^(5A), in particular adjacent radicals, together    with the atoms connecting them may be joined to form a preferably    five-, six- or seven-membered ring or a preferably five-, six- or    seven-membered heterocycle which contains at least one atom selected    from the group consisting of N, P, O and S, where-   R^(8A) are identical or different and can each be C₁-C₁₀-alkyl,    C₃-C₁₀-cycloalkyl, C₆-C₁₅-aryl, C₁-C₄-alkoxy or C₆-C₁₀-aryloxy and-   Z^(A) is as defined for X^(A) or is

where the radicals

-   R^(9A) to R^(13A) are each, independently of one another, hydrogen,    C₁-C₂₂-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may    in turn bear C₁-C₁₀-alkyl groups as substituents, C₂-C₂₂-alkenyl,    C₆-C₂₂-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, —NR^(14A) ₂,    —N(SiR^(14A) ₃)₂, —OR^(14A), —OSiR^(14A) ₃, —SiR^(14A) ₃, where the    radicals R^(1A) to R^(5A) may also be substituted by halogen and/or    two radicals R^(1A) to R^(5A), in particular adjacent radicals,    together with the atoms connecting them may be joined to form a    preferably five-, six- or seven-membered ring or a preferably five-,    six- or seven-membered heterocycle which contains at least one atom    selected from the group consisting of N, P, O and S, where-   R^(14A) are identical or different and can each be C₁-C₁₀-alkyl,    C₃-C₁₀-cycloalkyl, C₆-C₁₅-aryl, C₁-C₄-alkoxy or C₈-C₁₀-aryloxy,    or the radicals R^(4A) and Z^(A) together form an —R^(15A) _(v) _(A)    -A^(A)-group, where-   R^(15A)is

where

-   R^(16A), R^(17A) and R^(18A) are identical or different and are each    a hydrogen atom, a halogen atom, a trimethylsilyl group, a    C₁-C₁₀-alkyl group, a C₁-C₁₀-fluoroalkyl group, a C₆-C₁₀-fluoroaryl    group, a C₆-C₁₀-aryl group, a C₁-C₁₀-alkoxy group, a    C₇-C₁₅-alkylaryloxy group, a C₂-C₁₀-alkenyl group, a    C₇-C₄₀-arylalkyl group, a C₈-C₄₀-arylalkenyl group or a    C₇-C₄₀-alkylaryl group or two adjacent radicals together with the    atoms connecting them form a saturated or unsaturated ring having    from 4 to 15 carbon atoms, and-   M^(2A) is silicon, germanium or tin, preferably silicon,-   A^(A) is —O—, —S—, —NR^(19A), —PR^(19A), —O—R^(19A), —NR^(19A) ₂,    —PR^(19A) ₂    -   or an unsubstituted, substituted or fused, heterocyclic ring        system, where-   R^(19A) are each, independently of one another, C₁-C₁₀-alkyl,    C₆-C₁₅-aryl, C₃-C₁₀-cycloalkyl, C₇-C₁₈-alkylaryl or —Si(R^(20A))₃,-   R^(20A) is hydrogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl which may in turn    bear C₁-C₄-alkyl groups as substituents or C₃-C₁₀-cycloalkyl,-   V^(A) is 1 or, if A^(A) is an unsubstituted, substituted or fused,    heterocyclic ring system, 1 or 0    or the radicals R^(4A) and R^(12A) together form an —R^(15A)— group.

It is preferred that the radicals X^(A) in the formula (I) areidentical, preferably fluorine, chlorine, bromine, C₁-C₇-alkyl orarylalkyl, in particular chlorine, methyl or benzyl.

Among the organic transition metal compounds of the formula (I),preference is given to

Among the compounds of the formula (Ia); particular preference is givento those in which

-   M^(1A) is titanium or chromium,-   X^(A) is chlorine, C₁-C₄-alkyl, phenyl, alkoxy or aryloxy,-   n^(A) is 1 or 2 and-   R^(1A) to R^(5A) are each hydrogen or C₁-C₄-alkyl or two adjacent    radicals R^(1A) to R^(5A) together with the atoms connecting them    form a substituted or unsubstituted unsaturated six-membered ring.

Among the metallocenes of the formula (Ib), preference is given to thosein which

-   M^(1A) is titanium, zirconium, hafnium or chromium,-   X^(A) is chlorine, C₁-C₄-alkyl or benzyl, or two radicals X form a    substituted or unsubstituted butadiene ligand,-   n^(A) is 1 or 2, preferably 2, or, if M^(1A) is chromium, 0,-   R^(1A) to R^(5A) are each hydrogen, C₁-C₈-alkyl, C₆-C₁₀-aryl,    —NR^(8A) ₂, —OSiR^(8A) ₃, SiR^(8A) ₃ or —Si(R^(8A))₃ and-   R^(9A) to R^(13A) are each hydrogen, C₁-C₈-alkyl, C₆-C₁₀-aryl,    —NR^(8A) ₂, —OSiR^(8A) ₃, —SiR^(8A) ₃ or —Si(R^(8A))₃    or in each case two radicals R^(1A) to R^(5A) and/or R^(9A) to    R^(13A) together with the cyclopentadienyl ring form an indenyl or    substituted indenyl system.

Particularly useful compounds of the formula (Ib) are those in which thecyclopentadienyl radicals are identical.

Examples of particularly useful compounds of the formula (Ib) are

-   bis(cyclopentadienyl)zirconium dichloride,-   bis(pentamethylcyclopentadienyl)zirconium dichloride,-   bis(methylcyclopentadienyl)zirconium dichloride,-   bis(ethylcyclopentadienyl)zirconium dichloride,-   bis(n-butylcyclopentadienyl)zirconium dichloride,-   bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride,-   bis(indenyl)zirconium dichloride,-   bis(tetrahydroindenyl)zirconium dichloride and-   bis(trimethylsilylcyclopentadienyl)zirconium dichloride    and also the corresponding dimethylzirconium compounds.

Particularly useful metallocenes of the formula (Ic) are those in which

-   R^(1A) and R^(9A) are identical or different and are each hydrogen    or a C₁-C₁₀-alkyl group,-   R^(5A) and R^(13A) are identical or different and are each hydrogen    or a methyl, ethyl, isopropyl or tert-butyl group,-   R^(3A) and R^(11A) are each C₁-C₄-alkyl and-   R^(2A) and R^(10A) are each hydrogen    or    two adjacent radicals R^(2A) and R^(3A) or R^(10A) and R^(11A)    together form a saturated or unsaturated cyclic group having from 4    to 44 carbon atoms,-   R^(15A) is -M^(2A)R^(16A)R^(17A)— or    —CR^(16A)R^(17A)—CR^(16A)R^(17A)— or —BR^(16A)— or    —BNR^(16A)R^(17A)—,-   M^(1A) is titanium, zirconium or hafnium and-   X^(A) are identical or different and are each chlorine, C₁-C₄-alkyl,    benzyl, phenyl or C₇-C₁₅-alkylaryloxy.

Particularly useful compounds of the formula (Ic) are those of theformula (Ic′)

where

-   the radicals R^(A) are identical or different and are each hydrogen,    C₁-C₁₀-alkyl or C₃-C₁₀-cycloalkyl, preferably methyl, ethyl,    isopropyl or cyclohexyl, C₆-C₂₀-aryl, preferably phenyl, naphthyl or    mesityl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, preferably    4-tert-butylphenyl or 3,5-di-tert-butylphenyl, or    C₈-C₄₀-arylalkenyl,-   R^(5A) and R^(13A) are identical or different and are each hydrogen,    C₁-C₆-alkyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl,    n-hexyl or tert-butyl,    and the rings S and T are identical or different saturated,    unsaturated or partially saturated.

The indenyl or tetrahydroindenyl ligands of the metallocenes of theformula (Ic′) are preferably substituted in the 2 position, the 2,4positions, the 4,7 positions, the 2,4,7 positions, the 2,6 positions,the 2,4,6 positions, the 2,5,6 positions, the 2,4,5,6 positions or the2,4,5,6,7 positions, in particular in the 2,4 positions, with thefollowing nomenclature being employed for the site of substitution:

As complexes (Ic′), preference is given to using bridged bisindenylcomplexes in the rac or pseudo-rac form. For the present purposes, thepseudo-rac form refers to complexes in which the two indenyl ligands arein the rac arrangement relative to one another when all othersubstituents of the complex are disregarded.

Examples of particularly useful metallocenes (Ic) and (Ic′) are

-   dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride,-   dimethylsilanediylbis(indenyl)zirconium dichloride,-   dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride,-   ethylenebis(cyclopentadienyl)zirconium dichloride,-   ethylenebis(indenyl)zirconium dichloride,-   ethylenebis(tetrahydroindenyl)zirconium dichloride,-   tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride,-   dimethylsilanediylbis(3-tert-butyl-5-methylcyclopentadienyl)zirconium    dichloride,-   dimethylsilanediylbis(3-tert-butyl-5-ethylcyclopentadienyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methylindenyl)zirconium dichloride,-   dimethylsilanediylbis(2-isopropylindenyl)zirconium dichloride,-   dimethylsilanediylbis(2-tert-butylindenyl)zirconium dichloride,-   diethylsilanediylbis(2-methylindenyl)zirconium dibromide,-   dimethylsilanediylbis(3-methyl-5-methylcyclopentadienyl)zirconium    dichloride,-   dimethylsilanediylbis(3-ethyl-5-isopropylcyclopentadienyl)zirconium    dichloride,-   dimethylsilanediylbis(2-ethylindenyl)zirconium dichloride,-   dimethylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride-   dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium dichloride-   methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium    dichloride,-   methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium    dichloride,-   diphenylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride,-   diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium dichloride,-   diphenylsilanediylbis(2-methylindenyl)hafnium dichloride,-   dimethylsilanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride,-   dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride,-   dimethylsilanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-propyl-4-(1-naphthyl)indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-i-butyl-4-(1-naphthyl)indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-propyl-4-(9-phenanthryl)indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4-isopropylindenyl)zirconium    dichloride,-   dimethylsilanediylbis(2,7-dimethyl-4-isopropylindenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4-[p-trifluoromethylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4-[3′,5′-dimethylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   diethylsilanediylbis(2-methyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-ethyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-propyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-n-butyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediylbis(2-hexyl-4-[4′-tert-butylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-phenylindenyl)-(2-methyl-4-phenylindenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-(1-naphthyl)indenyl)-(2-methyl-4-(1-naphthyl)indenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)-(2-methyl-4-[4′-tert-butylphenyl]-indenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)-(2-ethyl-4-[4′-tert-butylphenyl]-indenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)-(2-methyl-4-[3′,5′-bis-tert-buthylphenyl]indenyl)zirconium    dichloride,-   dimethylsilanediyl(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)-(2-methyl-4-[1′-naphthyl]indenyl)-zirconium    dichloride and-   ethylene(2-isopropyl-4-[4′-tert-butylphenyl]indenyl)-(2-methyl-4-[4′-tert-butylphenyl]indenyl)-zirconium    dichloride    and the corresponding dimethylzirconium,    monochloromono(alkylaryloxy)zirconium and di-(alkylaryloxy)zirconium    compounds.

Particularly useful compounds of the formula (Id) are those in which

-   M^(1A) is titanium or zirconium, in particular titanium, and-   X^(A) is chlorine, C₁-C₄-alkyl or phenyl or two radicals X together    form a substituted or unsubstituted butadiene ligand,-   R^(15A) is —SiR^(16A)R^(17A) or —CR^(16A)R^(17A)—CR^(16A)R^(17A)—,    and-   A^(A) is —O—, —S— or —NR^(19A)—,-   R^(1A) to R^(3A) and R^(5A) are each hydrogen, C₁-C₁₀-alkyl,    preferably methyl, C₃-C₁₀-cycloalkyl, C₆-C₁₅-aryl or —Si(R^(8A))₃,    or two adjacent radicals form a cyclic group having from 4 to 12    carbon atoms, with particular preference being given to all R^(1A)    to R^(3A) and R^(5A) being methyl.

Another group of compounds of the formula (Id) which are particularlyuseful are those in which

-   M^(1A) is titanium or chromium, preferably in the oxidation state    III and-   X^(A) is chlorine, C₁-C₄-alkyl or phenyl or two radicals X^(A) form    a substituted or unsubstituted butadiene ligand,-   R^(15A) is —SiR^(16A)R^(17A)— or —CR^(16A)R^(17A)—CR^(18A)R^(17A)—,    and-   A^(A) is —O—R^(19A), —NR^(19A) ₂, —PR^(19A) ₂,-   R^(1A) to R^(3A) and R^(5A) are each hydrogen, C₁-C₁₀-alkyl,    C₃-C₁₀-cloalkyl, C₆-C₁₅-arly or —Si(R^(8A))₃, or two adjacent    radicals form a cyclic group having from 4 to 12 carbon atoms.

The synthesis of such complexes can be carried out by methods known perse, with preference being given to the reaction of the appropriatelysubstituted, cyclic hydrocarbon anions with halides of titanium,zirconium, hafnium, vanadium, niobium, tantalum or chromium.

Examples of appropriate preparative methods are described, for example,in Journal of Organometallic Chemistry, 369 (1989), 359-370.

Further suitable organic transition-metal compounds A) are metalloceneshaving at least one ligand which is formed by a cyclopentadienyl orheterocyclopentadienyl and a fused-on heterocycle. In the heterocycles,at least one carbon atom is replaced by a heteroatom, preferably fromgroup 15 or 16 of the Periodic Table and in particular nitrogen orsulfur. Such compounds are described, for example, in WO 98/22486. Theseare, in particular,

-   dimethylsilanediyl(2-methyl-4-phenylindenyl)-(2,5-dimethyl-N-phenyl-4-azapentalene)zirconium    dichloride,-   dimethylsilanediylbis(2-methyl-4-phenyl-4-hydroazulenyl)zirconium    dichloride and-   dimethylsilanediylbis(2-ethyl-4-phenyl-4-hydroazulenyl)zirconium    dichloride.

Further examples of organic transition metal compounds A) which aresuitable for the purposes of the present invention are transition metalcomplexes with at least one ligand of the formulae (IIa) to (IIe),

where the transition metal is selected from among the elements Ti, Zr,Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt or is an element of therare earth metals. Preference is given to compounds containing nickel,iron, cobalt or palladium as central metal.

-   E^(B) is an element of group 15 of the Periodic Table of the    Elements, preferably N or P, particularly preferably N. The two or    three atoms E^(B) in a molecule can be identical or different

The radicals R^(1B) to R^(19B), which can be identical or differentwithin a ligand system of the formulae (IIa) to (IIe), have thefollowing meanings:

-   R^(1B) and R^(4B) are, independently of one another, hydrocarbon or    substituted hydrocarbon radicals, preferably hydrocarbon radicals in    which the carbon atom adjacent to the element E^(B) is connected to    at least two carbon atoms,-   R^(2B) and R^(3B) are each, independently of one another, hydrogen    or a hydrocarbon or substituted hydrocarbon radical, where R^(2B)    and R^(3B) may also together form a ring system in which one or more    heteroatoms may be present,-   R^(6B) and R^(8B) are, independently of one another, hydrocarbon or    substituted hydrocarbon radicals,-   R^(5B) and R^(9B) are each, independently of one another, hydrogen    or a hydrocarbon or substituted hydrocarbon radical,    where R^(6B) and R^(5B) or R^(8B) and R^(9B) may also together form    a ring system,-   R^(7B) are each, independently of one another, hydrogen or a    hydrocarbon or substituted hydrocarbon radical, where two R^(7A) may    also together form a ring system,-   R^(10B) and R^(14B) are, independently of one another, hydrocarbon    or substituted hydrocarbon radicals,-   R^(11B), R^(12B), R^(12B)′ and R^(13B) are each, independently of    one another hydrogen or a hydrocarbon or substituted hydrocarbon    radical, where two or more geminal or vicinal radicals R^(11B),    R^(12B), R^(12B)′ and R^(13B) may also together form a ring system,-   R^(15B) and R^(18B) are each, independently of one another, hydrogen    or a hydrocarbon or substituted hydrocarbon radical,-   R^(16B) and R^(17B) are each, independently of one another, hydrogen    or a hydrocarbon or substituted hydrocarbon radical,-   R^(19B) is an organic radical which forms a 5- to 7-membered    substituted or unsubstituted, in particular unsaturated or aromatic,    heterocyclic ring system, in particular together with E^(B) a    pyridine system,-   n^(1B) is 0 or 1, with compounds of the formula (IIc) in which    n^(1B) is 0 being negatively charged, and-   n^(2B) is an integer from 1 to 4, preferably 2 or 3

Particularly useful transition metal complexes with ligands of theformulae (IIa) to (IId) are, for example, complexes of the transitionmetals Fe, Co, Ni, Pd or Pt with ligands of the formula (IIa).Particular preference is given to diimine complexes of Ni or Pd, e.g.:

-   di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienepalladium    dichloride,-   di(di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel dichloride,-   di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienedimethylpalladium,-   di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienedimethylnickel,-   di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium    dichloride,-   di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel dichloride,-   di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienedimethylpalladium,-   di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienedimethylnickel,-   di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride,-   di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel dichloride,-   di(2-methylphenyl)-2,3-dimethyldiazabutadienedimethylpalladium,-   di(2-methylphenyl)-2,3-dimethyldiazabutadienedimethylnickel;-   diphenyl-2,3-dimethyldiazabutadienepalladium dichloride,-   diphenyl-2,3-dimethyldiazabutadienenickel dichloride,-   diphenyl-2,3-dimethyldiazabutadienedimethylpalladium,-   diphenyl-2,3-dimethyldiazabutadienedimethylnickel,-   di(2,6-dimethylphenyl)azanaphthenepalladium dichloride,-   di(2,6-dimethylphenyl)azanaphthenenickel dichloride,-   di(2,6-dimethylphenyl)azanaphthenedimethylpalladium,-   di(2,6-dimethylphenyl)azanaphthenedimethylnickel,-   1,1′-bipyridylpalladium dichloride,-   1,1′-bipyridylnickel dichloride,-   1,1′-bipyridyldimethylpalladium or-   1,1′-bipyridyldimethylnickel.

Particularly useful compounds (IIe) are those which are described in J.Am. Chem. Soc. 120, p. 4049 ff. (1998), J. Chem. Soc., Chem. Commun.1998, 849. As complexes containing ligands (IIe), preference is given tousing 2,6-bis(imino)pyridyl complexes of the transition metals Fe, Co,Ni, Pd or Pt, in particular Fe.

As organic transition metal compounds A), it is also possible to useiminophenoxide complexes whose ligands are prepared, for example, fromsubstituted or unsubstituted salicylaldehydes and primary amines, inparticular substituted or unsubstituted arylamines. Transition metalcomplexes with pi ligands which contain one or more heteroatoms in thepi system, for example the boratabenzene ligand, the pyrrolyl anion orthe phospholyl anion, can also be used as organic transition metalcompounds A).

Further transition metal compounds A) which are suitable for thepurposes of the present invention are substituted monocyclopentadienyl,monoindenyl, monofluorenyl or heterocyclopentadienyl complexes ofchromium, molybdenum or tungsten in which at least one of thesubstituents on the cyclopentadienyl ring bears a rigid donor functionwhich is not bound exclusively via sp³-hybridized carbon or siliconatoms. The most direct link to the donor function contains at least onesp- or sp²-hybridized carbon atom, preferably from one to threesp²-hybridized carbon atoms. The direct link preferably comprises anunsaturated double bond, an aromatic or together with the donor forms apartially unsaturated or aromatic heterocyclic system.

In these transition metal compounds, the cyclopentadienyl ring can alsobe a heterocyclopentadienyl ligand, i.e. at least one carbon atom canalso be replaced by a heteroatom from group 15 or 16. In this case,preference is given to a carbon atom in the C₅-ring being replaced byphosphorus. In particular, the cyclopentadienyl ring is substituted byfurther alkyl groups which can also form a five- or six-membered ring,e.g. tetrahydroindenyl, indenyl, benzindenyl or fluorenyl.

Possible donors are uncharged functional groups containing an element ofgroup 15 or 16 of the Periodic Table, e.g. amine, imine, carboxamide,carboxylic ester, ketone (oxo), ether, thioketone, phosphine, phosphite,phosphine oxide, sulfonyl, sulfonamide, or unsubstituted, substituted orfused, partially unsaturated heterocyclic or heteroaromatic ringsystems.

Preference is here given to using substituted monocyclopentadienyl,monoindenyl, monofluorenyl or heterocyclopentadienyl complexes of theformula (III)

where

-   M^(C) is chromium, molybdenum or tungsten and-   Z^(C) has the formula (IIIa)

where the variables have the following meanings:

-   E^(1C)-E^(5C) are each carbon or, for not more than one atom E^(1C)    to E^(5C), phosphorus or nitrogen,-   A^(C) is —NR^(5C)R^(6C), —PR^(5C)R^(8C), —OR^(5C), —SR^(5C) or an    unsubstituted, substituted or fused, partially unsaturated    heterocyclic or heteroaromatic ring system,-   R^(C) is one of the following groups:

-   -   or, if A^(C) is an unsubstituted, substituted or fused,        partially unsaturated heterocyclic or heteroaromatic ring        system, may also be

where

-   L^(1C), L^(2C) are each silicon or carbon,-   X^(C) is 1 or, if A^(1C) is an unsubstituted, substituted or fused,    partially unsaturated heterocyclic or heteroaromatic ring system,    may also be 0,-   X^(C) are each, independently of one another, fluorine, chlorine,    bromine, iodine, hydrogen, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,    C₆-C₂₀-aryl, C₇-C₄₀-alkylaryl, —NR^(15C)R^(16C), —OR^(15C),    —SR^(15C), —SO₃R^(15C), —OC(O)R^(15C), —CN, —SCN, β-diketonate, —CO,    BF₄ ⁻, PF₆ ⁻ or a bulky noncoordinating anion,-   R^(1C)-R^(16C) are each, independently of one another, hydrogen,    C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₆-C₂₀-aryl, C₇-C₄₀-alkylaryl,    alkylaryl having from 1 to 10 carbon atoms in the alkyl part and    6-20 carbon atoms in the aryl part, SiR^(17C) ₃, where the organic    radicals R^(1B)-R^(16B) may also be substituted by halogens and two    geminal or vicinal radicals R^(1C)-R^(16C) may also be joined to    form a five- or six-membered ring,-   R^(17C) are each, independently of one another, hydrogen,    C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₆-C₂₀-aryl, C₇-C₄₀-alkylaryl, and two    geminal radicals R^(17C) may also be joined to form a five- or    six-membered ring,-   n^(C) is 1, 2 or 3 and-   m^(C) is 1, 2 or 3.

The transition metal M^(C) is particularly preferably chromium.

Examples of organic transition metal compounds of the formula (III) are

-   1-(8-quinolyl)-2-methyl-4-methylcyclopentadienylchromium(III)    dichloride,-   1-(8-quinolyl)-3-isopropyl-5-methylcyclopentadienylchromium(III)    dichloride,-   1-(8-quinolyl)-3-tert-butyl-5-methylcyclopentadienylchromium(III)    dichloride,-   1-(quinolyl)-2,3,4,5-tetramethylcyclopentadienylchromium(III)    dichloride,-   1-(8-quinolyl)tetrahydroindenylchromium(III) dichloride,-   1-(8-quinolyl)indenylchromium(III) dichloride,-   1-(8-quinolyl)-2-methylindenylchromium(III) dichloride,-   1-(8-quinolyl)-2-isopropylindenylchromium(III) dichloride,-   1-(8-quinolyl)-2-ethylindenylchromium(III) dichloride,-   1-(8-quinolyl)-2-tert-butylindenylchromium(III) dichloride,-   1-(8-quinolyl)benzindenylchromium(III) dichloride,-   1-(8-quinolyl)-2-methylbenzindenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))-2-methyl-4-methylcyclopentadienylchromium(III)    dichloride,-   1-(8-(2-methylquinolyl))-2,3,4,5-tetramethylcyclopentadienylchromium(III)    dichloride,-   1-(8-(2-methylquinolyl))tetrahydroindenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))indenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))-2-methylindenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))-2-isopropylindenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))-2-ethylindenylchromium(III) dichloride,-   1-(8-(2-methylquinolyl))-2-tert-butylindenylchromium(III)    dichloride,-   1-(8-(2-methylquinolyl))benzindenylchromium(III) dichloride or-   1-(8-(2-methylquinolyl))-2-methylbenzindenylchromium(III)    dichloride.

The preparation of functional cyclopentadienyl ligands has been knownfor a long time. Various synthetic routes for these complexing ligandsare described, for example, by M. Enders et al. in Chem. Ber. (1996),129, 459-463, or P. Jutzi und U. Slemeling in J. Orgmet. Chem. (1995),500, 175-185.

The metal complexes, in particular the chromium complexes, can beobtained in a simple manner by reacting the corresponding metal salts,e.g. metal chlorides, with the ligand anion (e.g. by a method analogousto the examples in DE-A 197 10 615).

Further transition metal compounds A) which are suitable for thepurposes of the present invention are imidochromium compounds of theformula (IV),

where the variables have the following meanings:

-   R^(D) is R^(1D)C═NR^(2D), R^(1D)C═O, R^(1D)C═O(OR^(2D)), R^(1D)C═S,    (R^(1D))₂P═O, (OR^(1D))₂P═O, SO₂R¹⁰ , R^(1D)R^(2D)C═N, NR^(1D)R^(2D)    or BR^(1D)R^(2D), C₁-C₂₀-alkyl, C₁-C₂₀-cycloalkyl, C₂-C₂₀-alkenyl,    C₆-C₂₀-aryl, C₇-C₄₀-alkylaryl, hydrogen if this is bound to a carbon    atom, where the organic radicals R^(1D) and R^(2D) may also bear    inert substituents,-   X^(D) are each, independently of one another, fluorine, chlorine,    bromine, iodine, —NR^(3D)R^(4D), —NP(R^(3D))₃, —OR^(3D),    —OSi(R^(3D))₃, —SO₃R^(3D), —OC(O)R^(3D), β-diketonate, BF₄ ⁻, PF₈ ⁻    or a bulky weakly coordinating or noncoordinating anion,-   R^(1D)-R^(4D) are each, independently of one another, C₁-C₂₀-alkyl,    C₂-C₂₀-alkenyl, C₆-C₂₀-aryl, C₇-C₄₀-alkylaryl; hydrogen if this is    bound to a carbon atom, where the organic radicals R^(1D) to R^(4D)    may also bear inert substituents,-   n^(D) is 1 or 2,-   m^(D) is 1, 2 or 3, where m^(1D) is such that the metallocene    complex of the formula (IV) is uncharged for the given valence of    Cr,-   L^(D) is an uncharged donor, and-   y^(D) is from 0 to 3.

Such compounds and their preparation are described, for example, in WO01/09148.

Further suitable organic transition metal compounds A) are transitionmetal complexes with a tridentate macrocyclic ligand, e.g.

-   [1,3,5-tri(methyl)-1,3,5-triazacyclohexane]chromium trichloride,-   [1,3,5-tri(ethyl)-1,3,5-triazacyclohexane]chromium trichloride,-   [1,3,5-tri(octyl)-1,3,5-triazacyclohexane]chromium trichloride,-   [1,3,5-tri(dodecyl)-1,3,5-triazacyclohexane]chromium trichloride and-   [1,3,5-tri(benzyl)-1,3,5-triazacyclohexane]chromium trichloride.

Mixtures of various organic transition metal compounds can also be usedas component A).

A further component, namely component B), used in the preparation of thecatalyst is a mixture of at least two different organometalliccompounds. In the process of the present invention, the organictransition metal compound A) is firstly brought into contact with themixture of the organo metallic compounds.

Suitable organometallic compounds B) are ones of the formula (V),M¹(R¹)_(r)(R²)_(s)(R³)_(t)  (V)where

-   M¹ is an alkali metal, an alkaline earth metal or a metal of group    13 of the Periodic Table, i.e. boron, aluminum, gallium, indium or    thallium,-   R¹ is hydrogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl, halo-C₁-C₁₀-alkyl,    halo-C₆-C₁₅-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, C₁₀-C₁₀-alkoxy    or halo-C₇-C₄₀-alkylaryl, halo-C₇-C₄₀-arylalkyl or    halo-C₁-C₁₀-alkoxy,-   R² and R³ are each hydrogen, halogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl,    halo-C₁-C₁₀-alkyl, halo-C₆-C₁₅-aryl, C₇-C₄₀-arylalkyl,    C₇-C₄₀-alkylaryl, C₁-C₁₀-alkoxy or halo-C₇-C₄₀-alkylaryl,    halo-C₇-C₄₀-arylalkyl or halo-C₁-C₁₀-alkoxy,-   r is an integer from 1 to 3    and-   s and t are integers from 0 to 2, where the sum r+s+t corresponds to    the valence of M¹.

Among the metal compounds of the formula (V) preference is given tothose in which

-   M¹ is lithium, magnesium or aluminum and-   R¹, R² and R³ are each hydrogen or C₁-C₁₀-alkyl.

Particularly preferred metal compounds of the formula (M) aren-butyllithium, n-butyl-n-octylmagnesium, n-butyl-n-heptylmagnesium,triphenylaluminum, triisoprenaluminum, tri-n-octyl-aluminum,tri-n-hexylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-propylaluminum, tri-isopropylatuminum, triethylaluminum ortrimethylaluminum.

Furthermore, in the preparation of the catalyst, It is also possible toadd the component B) or portions of the component B) in further steps inthe catalyst preparation, i.e. apart from the reaction of the organictransition metal compound A) with the mixture of the organometalliccompounds B), there can be an additional addition ofindividual-organometallic compounds, for example of the formula (V), orof mixtures of organometallic compounds.

As component C) in the preparation according to the present invention ofthe catalyst, use is made of at least one cation-forming compound.Suitable cation-forming compounds are, for example, strong unchargedLewis acids, ionic compounds having Lewis-acid cations, ionic compoundscontaining Brönsted acids as cations or compounds of the aluminoxanetype. The cation-forming compounds are frequently also referred to ascompounds capable of forming metallocenium ions.

As strong uncharged Lewis acids, preference is given to compounds of theformula (VI)M²X¹X²X³  (VI)where

-   M² is an element of group 13 of the Periodic Table of the Elements,    in particular B, Al or Ge and preferably B, and-   X¹, X² and X³ are each hydrogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl,    alkylaryl, arylalkyl, haloalky or haloaryl each having from 1 to 10    carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in    the aryl radical or fluorine, chlorine, bromine or iodine, in    particular haloaryl, preferably pentafluorophenyl.

Further examples of strong, uncharged Lewis acids are mentioned in WO00/31090.

Particular preference is given to compounds of the formula (VI) in whichX¹, X² and X³ are identical, preferably tris(pentafluorophenyl)borane.

Suitable ionic compounds having Lewis-acid cations are salt-likecompounds of the cation of the formula (VII)[(Y^(a+))Q₁Q₂ . . . Q_(z)]^(d+)  (VII)where

-   Y is an element of groups 1 to 16 of the Periodic Table of the    Elements,-   Q₁ to Q_(z) are singly negatively-charged groups such as    C₁-C₂₈-alkyl, C₆-C₁₅-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl    each having from 6 to 20 carbon atoms in the aryl radical and from 1    to 28 carbon atoms in the alkyl radical, C₃-C₁₀-cycloalkyl which may    bear C₁-C₁₀-alkyl groups as substituents, halogen, C₁-C₂₈-alkoxy,    C₅-C₁₅-aryloxy, silyl groups or mercaptyl groups,-   a is an integer from 1 to 6 and-   z is an integer from 0 to 5,-   d corresponds to the difference a−z, but d is greater than or equal    to 1.

Particularly useful cations are carbonium cations, oxonium cations andsulfonium cations and also cationic transition metal complexes.Particular mention may be made of the triphenylmethyl cation, the silvercation and the 1,1′-dimethylferrocenyl cation. They preferably havenoncoordinating counterions, in particular boron compounds as arementioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.

Salts having noncoordinating anions can also be prepared by combining aboron or aluminum compound, e.g. an aluminum alkyl, with a furthercompound which can react to link two or more boron or aluminum atoms,e.g. water, and a third compound which forms an ionizing ionic compoundwith the boron or aluminum compound, e.g. triphenylchloromethane. Inaddition, a fourth compound which likewise reacts with the boron oraluminum compound, e.g. pentafluorphenol, can also be added.

Ionic compounds containing Brönsted acids as cations preferably likewisehave noncoordinating counterions. As Brönsted acid, particularpreference is given to protonated amine or aniline derivatives.Preferred cations are N,N-dimethylanilinium,N,N-dimethylcyclohexylammonium and N,N-dimethylbenzylammonium andderivatives of the last two.

Preferred ionic cation-forming compounds are, in particular,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)-borate andN,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

It is also possible for two or more borate anions to be joined to oneanother, as in the dianion [(C₆F₅)₂B—C₆F₄—B(C₆F₅)₂]²⁻, or the borateanion can be bound to the support surface via a bridge having a suitablefunctional group.

Further suitable cation-forming compounds are listed in WO 00/31090.

Suitable cation-forming compounds of the abovementioned types can alsobe obtained, for example, by reaction of organometallic compounds withorganic compounds containing at least one functional group containingactive hydrogen. Examples of suitable functional groups in the organiccompounds are hydroxyl groups, primary and secondary amino groups,mercapto groups, silanol groups, carboxyl groups, amido groups or imidogroups, with hydroxyl groups being preferred.

Preferred organic compounds containing hydroxyl groups are, inparticular, those of the formula (VIII),(R⁴)_(x)-A-OH)_(y)  (VIII)where

-   A is an atom of main group 13, 14 or 15 of the Periodic Table or a    group comprising from 2 to 20 carbon atoms, preferably an atom of    main group 13 of the Periodic Table, in particular boron or    aluminum, or a partially halogenated or perhalogenated C₁-C₂₀-alkyl    or C₆-C₄₀-aryl group and is particularly preferably an atom of main    group 13 of the Periodic Table, preferably boron or aluminum and in    particular boron,-   R⁴ are identical or different and are each, independently of one    another, hydrogen, halogen, C₁-C₂₀-alkyl, C₁-C₂₀-haloalkyl,    C₁-C₁₀-alkoxy, C₆-C₂₀-aryl, C₆-C₂₀-haloaryl, C₈-C₂₀-aryloxy,    C₇-C₄₀-arylalkyl, C₇-C₄₀-haloarylalkyl, C₇-C₄₀-alkylaryl or    C₇-C₄₀-haloalkylaryl or R⁴ is an OSiR₃ ⁵ group, where-   R⁵ are identical or different and are each hydrogen, halogen,    C₁-C₂₀-alkyl, C₁-C₂₀-haloalkyl, C₁-C₁₀-alkoxy, C₆-C₂₀-aryl,    C₆-C₂₀-haloaryl, C₆-C₂₀-aryloxy, C₇-C₄₀-arylalky,    C₇-C₄₀-haloarylalkyl, C₇-C₄₀-alkylaryl or C₇-C₄₀-haloalkylaryl,    -   and R⁴ is preferably hydrogen, halogen, C₆-C₁₄-aryl,        C₆-C₁₄-haloaryl, C₁-C₁₄-alkyl, C₁, C₁₄-haloalkyl,        C₇-C₃₀-arylalkyl, C₇-C₃₀-haloarylalkyl, C₇-C₃₀-alkylaryl or        C₇-C₃₀-haloalkylaryl and    -   is particularly preferably C₆-C₁₀-aryl, C₆-C₁₀-haloaryl,        C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₇-C₂₀-alkylaryl or        C₇-C₂₀-haloalkylaryl,-   y is at least 1 and is preferably from 1 to 5, in particular 1 or 2    and very particularly preferably 1, and-   x is an integer from 0 to 41, with particular-preference being given    to x being 2 when y is 1 or being 1 when y is 2.

Examples of preferred compounds of the formula (VIII) are borinic acidsof the formula R⁴ ₂B(OH) or boronic acids of the formula R⁴B(OH)₂.

Preferred organic compounds containing hydroxyl groups also includecompounds having partially fluorinated or perfluorinated aryl groups,e.g. pentafluorophenol or nonafluorobiphenyl-1-ol ordihydroxyoctafluorobiphenyl. Such compounds C) can also be used in theform of an adduct with from 1 to 10 parts of water. These are thenpreferably compounds containing two OH groups, for example4,4′-dihydroxyoctafluorobiphenyl.(s.H₂O),1,2-dihydroxyoctafluorobiphenyl.(s.H₂O),1,8-dihydroxyhexafluoronaphthalene.(s.H₂O) or1,2-dihydroxyhexafluoronaphthalene.(s.H₂O), where s is from 1 to 10.

Suitable cation-forming compounds can be obtained from the organiccompounds having functional groups containing active hydrogen by, inparticular, reaction with organoaluminum compounds and particularlypreferably with trialkylaluminums.

The amount of strong, uncharged Lewis acids, ionic compounds havingLewis-acid cations or ionic compounds containing Brönsted acids ascations is preferably from 0.1 to 20 equivalents, preferably from 1 to10 equivalents, based on the organic transition metal compound.

As compounds of the aluminoxane type, it is possible to use, forexample, the compounds described in WO 00/31090. Particularly usefulcompounds of this type are open-chain or cyclic aluminoxane compounds ofthe formula (IX) or (X)

where

-   R⁶ is a C₁-C₄-alkyl group, preferably a methyl or ethyl group, and-   m is an integer from 5 to 30, preferably from 10 to 25.

These oligomeric aluminoxane compounds are usually prepared by reactionof a solution of trialkylaluminum with water. In general, the oligomericaluminoxane compounds obtained in this way are in the form of mixturesof both linear and cyclic chain molecules of various lengths, so that mis to be regarded as a mean. The aluminoxane compounds can also bepresent in admixture with other metal alkyls, preferably with aluminumalkyls.

Furthermore, in place of the aluminoxane compounds of the formula (IX)or (X), it is also possible to use modified aluminoxanes in which atleast some of the hydrocarbon radicals or hydrogen atoms are replaced byalkoxy, aryloxy, siloxy or amide groups.

It has been found to be advantageous to use the organic transition metalcompounds and the aluminoxane compounds in such amounts that the atomicratio of aluminum from the aluminoxane compounds to the transition metalfrom the organic transition metal compound is in the range from 10:1 to1000:1, preferably from 20:1 to 500:1 and in particular in the rangefrom 30:1 to 400:1.

It is also possible to use mixtures of all the abovementionedcation-forming compounds. Preferred mixtures comprise aluminoxanes, inparticular methylaluminoxane, and an ionic compound, in particular anionic compound containing the tetrakis(pentafluorophenyl)borate anion,and/or a strong uncharged Lewis acid, in particulartris(pentafluorophenyl)borane.

Both the organic transition metal compound and the caton-formingcompound are preferably used in a solvent, with aromatic hydrocarbonshaving from 6 to 20 carbon atoms, in particular xylenes and toluene,being preferred.

In a preferred embodiment of the process of the present invention, atleast one support is used as component D) for preparing the olefinpolymerization catalyst. Such supports are preferably finely dividedsupports which may be any organic or inorganic, inert solid. Inparticular, the support component D) can be a porous support such astalc, a sheet silicate, an in organic oxide or a finely divided polymerpowder.

Inorganic oxides suitable as supports may be found among oxides of theelements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Tableof the Elements. Preference is given to oxides or mixed oxides of theelements calcium, aluminum, silicon, magnesium or titanium and alsocorresponding oxide mixtures. Other inorganic oxides which can be usedon their own or in combination with the abovementioned oxidic supportsare, for example, ZrO₂ or B₂O₃. Preferred oxides are silicon dioxide, inparticular in the form of a silica gel or a pyrogenic silica, oraluminum oxide. A preferred mixed oxide is, for example, calcinedhydrotalcite.

The support materials used preferably have a specific surface area inthe range from 10 to 1000 m²/g, preferably from 50 to 500 m²/g and inparticular from 200 to 400 m²/g, and a pore volume in the range from 0.1to 5 ml/g, preferably from 0.5 to 3.5 ml/g and in particular from 0.8 to3.0 ml/g. The mean particle size of the finely divided supports isgenerally in the range from 1 to 500 μm, preferably from 5 to 350 μm andin particular from 10 to 100 μm.

The inorganic support can be subjected to a thermal treatment, e.g. forremoving adsorbed water. Such a drying treatment is generally carriedout at from 80 to 300° C., preferably from 100 to 200° C., and ispreferably carried out under reduced pressure and/or in a stream ofinert gas, for example nitrogen or argon. The inorganic support can alsobe calcined, in which case the concentration of OH groups on the surfaceis adjusted and the structure of the solid may be altered by a treatmentat from 200 to 1000° C. The support can also be treated chemically usingcustomary desiccants such as metal alkyls, preferably aluminum alkyls,chlorosilanes or SiCl₄, or else methyl-aluminoxane. Appropriatetreatment methods are described, for example, in WO 00/31090.

The inorganic support material can also be chemically modified. Forexample, the treatment of silica gel with NH₄SiF₈ leads to fluorinationof the silica gel surface and treatment of silica gels with silanescontaining nitrogen-, fluorine- or sulfur-containing groups givescorrespondingly modified silica gel surfaces.

Further possible support materials include finely divided polymerpowders, for example polyolefins such as polyethylene or polypropyleneor polystyrene. They should preferably be freed of any adheringmoisture, solvent residues or other impurities by appropriatepurification or drying operations before use. It is also possible to usefunctionalized polymeric supports, e.g. supports based on polystyrenes,via whose functional groups, for example ammonium or hydroxide groups,at least one of the catalyst components can be immobilized.

In a further preferred embodiment, at least one Lewis base is used ascomponent E). Suitable Lewis bases generally have the formula (XI),M³R⁶R⁷R⁸  (XI)where

-   R⁶, R⁷ and R⁸ are identical or different and are each a hydrogen    atom, a C₁-C₂₀-alkyl group, a C₁-C₂₀-haloalkyl group, a C₆-C₄₀-aryl    group, a C₆-C₄₀-haloaryl group, a C₇-C₄₀-alkylaryl group or a    C₇-C₄₀-arylalkyl group, preferably a C₇-C₄₀-arylalkyl group, where    two radicals or all three radicals R³, R⁴ and R⁵ may be joined to    one another via C₂-C₂₀ units,-   M³ is an element of group 15 of the Periodic Table of the Elements,-   R⁶, R⁷ and R⁸ are preferably C₁-C₂₀-alkyl, C₆-C₄₀-aryl or    C₇-C₄₀-alkylaryl. It is particularly preferred that at least one of    R⁶, R⁷ and R⁸ is a C₇-C₄₀-arylalkyl group, for example benzyl.-   M³ is preferably nitrogen or phosphorus, in particular nitrogen.

Examples of Lewis bases used as component E) are methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, tripropylamine, tributylamine,N,N-dimethylaniline, N,N-diethylaniline or N,N-dimethylcyclohexylamine.Particularly preferred Lewis bases are, for example, benzylamine,N-benzyldimethylamine, N-benzyldiethylamine, N-benzylbutylamine,N-benzyl-tert-butylamine, N′-benzyl-N,N-dimethylethylenediamine,N-benzylethylenediamine, N-benzylisopropylamine, N-benzylmethylamine,N-benzylethylamine, N-benzyl-1-phenylethylamine,N-benzyl-2-phenylethylamine or N-benzylpiperazine.

When a Lewis base E) is used, preference is given to this firstly beingreacted with the support and the support which has been modified in thisway then being brought into contact with the further components.

The process of the present invention for preparing the catalysts iscarried out by bringing the components A) to C) and, if desired, D) andE) into contact with one another in any order. All components can beadded individually in succession, but it is also possible for individualcomponents to be mixed with one another initially and these mixturesthen to be brought into contact with other mixtures and/or individualcomponents, provided that the organic transition metal compound A) isfirstly combined with the mixture of the organometallic compounds B)before the reaction product is then brought into contact with a furthercomponent or a mixture of further components of the catalyst.

A preferred way of bringing the components into contact with one anotheris firstly to bring the organic compound having at least one functionalgroup containing active hydrogen C) into contact with the organometalliccompound B), with a portion of the organometallic compound B) or, when amixture of different organometallic compounds is used, with at least oneof the constituents of the component B).

The components are usually combined in the presence of an organicsolvent in which the support D) which is preferably used, the reactionproducts of the support and/or the catalyst solid formed are suspended.Suitable solvents include aromatic or aliphatic solvents, for examplehexane, heptane, toluene or xylene or halogenated hydrocarbons such asmethylene chloride or halogenated aromatic hydrocarbons such aso-dichlorobenzene.

The components are generally combined at from −20° C. to 150° C.,preferably in the range from 0° C. to 100° C. When not all of thecomponents are brought into contact simultaneously, the temperature inthe individual steps of the combination can be the same. However, thetemperatures in the individual steps can also be different

The time for which the compounds which are being brought into contactwith one another are allowed to react is generally from 1 minute to 48hours. Preference is given to reaction times of from 10 minutes to 6hours. When the components are brought into contact with one another insteps, the reaction times in the individual steps are usually from 1minute to 6 hours and preferably from 10 minutes to 2 hours.

The ratios in which the components are preferably used are as follows:

The molar ratio of any Lewis base E) used to cation-forming compound C)is preferably from 0.05:1 to 2:1, in particular from 0.1:1 to 1:1.

The molar ratio of organic transition metal compound A) tocation-forming compound C) is preferably from 1:0.1 to 1:1000, inparticular from 1:1 to 1:100.

When a support D) is used, the catalyst solid can firstly beprepolymerized with α-olefins, preferably linear C₂-C₁₀-1-alkenes and inparticular ethylene or propylene, and the resulting prepolymerizedcatalyst solid can then be used in the actual polymerization. The massratio of catalyst solid used in the prepolymerization to polymerized-onmonomer is usually in the range from 1:0.1 to 1:200.

Furthermore, a small amount of an olefin, preferably an α-olefin, forexample vinylcyclohexane, styrene or phenyldimethylvinylsilane, asmodifying component, an antistatic or a suitable inert compound such asa wax or oil can be added as additive during or after the preparation ofa supported catalyst. The molar ratio of additives to organic transitionmetal compound A) is usually from 1:1000 to 1000:1, preferably from 1:5to 20:1.

The polymerization can be carried out in a known manner, in bulk, insuspension, in the gas phase or in a supercritical medium in thecustomary reactors used for the polymerization of olefins. It can becarried out batchwise or preferably continuously in one or more stages.Solution processes, suspension processes, stirred gas-phase processes orgas-phase fluidized-bed processes are all possible. As solvent orsuspension medium, it is possible to use inert hydrocarbons, for exampleisobutane, or else the monomers themselves.

The polymerizations can be carried out at from 60 to 300° C. andpressures in the range from 0.5 to 3000 bar. Preference is given totemperatures in the range from 50 to 200° C., in particular from 60 to100° C., and pressures in the range from 5 to 100 bar, in particularfrom 15 to 70 bar. The mean residence times are usually from 0.5 to 5hours, preferably from 0.5 to 3 hours. Molar mass regulators, forexample hydrogen, or customary additives such as antistatics can also beused in the polymerization.

The process of the present invention for preparing catalysts for olefinpolymerization is relatively simple and catalysts having a goodpolymerization activity can be prepared using a reduced amount ofexpensive starting materials such as transition metal compounds orboron-containing compounds. In particular, it is possible to use organictransition metal compounds having a low solubility in customary solventsfor preparing catalysts for olefin polymerization. It is also possibleto prepare catalysts having an increased polymerization activity.

EXAMPLES Example 1

a) Synthesis of the Supported Cocatalyst

5 ml of trimethylaluminum (2 M in toluene, 10 mmol) together with 45 mlof toluene were placed in a reaction vessel. At −10° C., a solution of 7g of bis(pentafluorophenyl)borinic acid (20 mmol) in 50 ml of toluenewas slowly added to the trimethylaluminum solution over a period of 15minutes. The mixture was brought to room temperature and stirred for onehour. 7 g of silica gel (XPO 2107, Grace) were suspended in 30 ml oftoluene, and 1.4 ml of N,N-dimethylbenzylamine were added to thissuspension at room temperature. The mixture was cooled to 0° C. and thesolution prepared above was slowly added. The mixture was subsequentlywarmed to mom temperature and stirred for 3 hours. The suspension wasthen filtered and the solid was washed with heptane. The residue wasdried to constant weight in an oil pump vacuum. This gave 11.2 g of awhite support material.

b) Application of the Organic Transition Metal Compound to the Support

250 μmol of trimethylaluminum (20% strength in a high-boilingdearomatized hydrocarbon mixture) and 250 μmol of triisobutylaluminum(20% strength in a high-boiling dearomatized hydrocarbon mixture) wereadded to a suspension of 37 mg of dimethylsilanediylbis(2-methyl(4′-tert-butylphenyl)indenyl)zirconium dichloride (50 μmol) in 25 ml oftoluene and the mixture was stirred at 50° C. for 1 hour. 2.2 g of thesupport prepared in Example 1a) were subsequently added at roomtemperature. The catalyst solution was stirred for 1 hour and thesolvent was then taken off in an oil pump vacuum. This resulted in anorange; free-flowing powder.

c) Polymerization

A dry 16 l reactor was flushed firstly with nitrogen and subsequentlywith propylene and then charged with 10 l of liquid propylene and 5standard liters of hydrogen. 13.3 ml of triisobutylaluminum (20%strength in a high-boiling dearomatized hydrocarbon mixture) were addedand the mixture was stirred for 15 minutes. 0.23 g of the catalyst solidprepared in Example 1b) were subsequently suspended in 20 ml of heptaneand introduced into the reactor via a lock and were rinsed in using 15ml of heptane. The reaction mixture was heated to the polymerizationtemperature of 65° C. and polymerized for 1 hour. This resulted in 1860g of pulverulent polypropylene, corresponding to a productivity of 8.1kg of PP/g of catalyst solid. The reactor had no deposits on theinterior wall or on the stirrer.

Comparative Example A

a) Synthesis of the Supported Cocatalyst

The supported cocatalyst prepared in Example 1a) was used.

b) Application of the Organic Transition Metal Compound to the Support

The procedure of Example 1b) was repeated using 500 μmol oftrimethylaluminum in place of the mixture of 250 μmol oftrimethylaluminum and 250 mmol of triisobutylaluminum. This resulted inan orange, free-flowing powder.

c) Polymerization

The polymerization was carried out as in Example 1c), but using 1.15 gof the catalyst solid prepared in comparative example Ab) in 20 ml ofheptane. This resulted in 3610 g of pulverulent polypropylene,corresponding to a productivity of 3.1 kg of PP/g of catalyst solid.After the polymerization, deposits were found on the interior wall ofthe reactor and on the stirrer.

Example 2

a) Catalyst Synthesis

30 mg ofdimethylsilanediylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride, 0.15 ml of triethylaluminum and 0.26 ml of a 20% strength byweight solution of triisobutylaluminum in a high-boiling dearomatizedhydrocarbon mixture were suspended in 20 ml of toluene and stirred at50° C. until a clear solution was obtained. The yellow solution wassubsequently brought to room temperature and admixed with 0.69 ml of a20% strength by weight solution of trimethylaluminum in a high-boilingdearomatized hydrocarbon mixture and 1 g ofbis(pentafluorophenyl)borinic acid. After stirring for one hour, 0.1 mlof dimethylbenzylamine was added, and after stirring for a further 30minutes, 2 g of silica gel (XPO 2107 from Grace) were added. Afterstirring for another 1 hour, the solvent was distilled off at 50° C.under reduced pressure. This gave 3.09 g of a salmon-colored,free-flowing powder.

b) Polymerization

A dry 2 l reactor was flushed firstly with nitrogen and subsequentlywith propylene and then charged with 1.5 l of liquid propylene. 3 ml ofa 20% strength by weight solution of triisobutylaluminum in ahigh-boiling dearomatized hydrocarbon mixture were added and the mixturewas stirred for 15 minutes. 250 mg of the catalyst system prepared inExample 2a) were subsequently suspended in 20 ml of heptane andintroduced into the reactor via a lock and were rinsed in using 15 ml ofheptane. The reaction mixture was heated to the polymerizationtemperature of 65° C. and polymerized for 1 hour. This resulted in 450 gof pulverulent polypropylene, corresponding to a productivity of 1.8 kgof PP/g of catalyst solid or an activity of 2.4 kg of PP/mmol of B or158 kg of PP/mmol of Zr×h. The reactor had no deposits on the interiorwall or on the stirrer.

Example 3

a) Catalyst Synthesis

0.69 ml of trimethylaluminum and 10 ml of toluene were placed in areaction vessel and admixed at room temperature with 1 g ofbis(pentafluorophenyl)borinic acid. After stirring at room temperaturefor one hour, 0.1 ml of dimethylbenzylamine were added and the mixturewas stirred for a further 15 minutes. A solution of 30 mg ofdimethylsilanediylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride, 0.15 ml of triethylaluminum and 0.26 ml oftriisobutylaluminum in 20 ml of toluene were subsequently added. Afterstirring at room temperature for 15 minutes, 2.5 g of silica gel (XPO2107 from Grace) were added and the mixture was stirred at roomtemperature for 1 hour. The solvent was subsequently distilled off at50° C. under reduced pressure. This gave 3.57 g of a salmon-red,free-flowing powder.

b) Polymerization

A dry 16 l reactor was flushed firstly with nitrogen and subsequentlywith propylene and then charged with 10 l of liquid propylene. 6 ml of a20% strength by weight solution of triisobutylaluminum in a high-boilingdearomatzed hydrocarbon mixture were added and the mixture was stirredfor 15 minutes. 5 standard liters of hydrogen were subsequently meteredin and the mixture was stirred for another 15 minutes. 250 mg of thecatalyst system prepared in Example 3a) were suspended in 20 ml ofheptane and introduced into the reactor via a lock and were rinsed inusing 15 ml of heptane. The reaction mixture was heated to thepolymerization temperature of 65° C. and polymerized for 1 hour. Thisresulted in 2.1 kg of pulverulent polypropylene, corresponding to aproductivity of 8.4 kg of PP/g of catalyst solid or an activity of 11 kgof PP/mmol of B or 740 kg of PP/mmol of Zr×h. The reactor had nodeposits on the interior wall or on the stirrer.

Example 4

a) Catalyst Synthesis

1.5 g of silica gel (XPO 2107 from Grace) were suspended in 20 ml oftoluene. Firstly 0.15 ml of a 20% strength by weight solution oftriethylaluminum and 0.26 ml of a 20% strength by weight solution oftriisobutylaluminum in a high-boiling dearomatized hydrocarbon mixtureand subsequently 30 mg ofdimethylsilanediylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride and 0.2 ml of dimethylbenzylamine were then added. Themixture was subsequently heated to 50° C. and stirred until a clearsolution was obtained. A mixture of 1 g of bis(pentafluorophenyl)borinicacid, 0.69 ml of a 20% strength by weight solution of trimethylaluminumin a high-boiling dearomatized hydrocarbon mixture and 10 ml of toluenewas added at room temperature. After stirring at room temperature for 1hour, the solvent was distilled off at 50° C. under reduced pressure.This gave 2.37 g of a salmon-colored, free-flowing powder.

b) Polymerization

A dry 2 l reactor was flushed firstly with nitrogen and subsequentlywith propylene and then charged with 1.5 l of liquid propylene. 3 ml ofa 20% strength by weight solution of triisobutylaluminum in ahigh-boiling dearomatized hydrocarbon mixture were added and the mixturewas stirred for 15 minutes. 250 mg of the catalyst system prepared inExample 4a) were subsequently suspended in 20 ml of heptane andintroduced into the reactor via a lock and rinsed in using 15 ml ofheptane. The reaction mixture was heated to the polymerizationtemperature of 65° C. and polymerized for 1 hour. This resulted in 169 gof pulverulent polypropylene, corresponding to a productivity of 0.7 kgof PP/g of catalyst solid or an activity of 0.6 kg of PP/mmol of B or 40kg of PP/mmol of Zr×h. The reactor had no deposits on the interior wallor on the stirrer.

1. A process for preparing a catalyst for olefin polymerizationcomprising the steps by bringing (A) at least one organic transitionmetal compound, (B) a mixture of at least two different organo metalliccompounds of formula (V),M¹(R¹)_(r)(R²)_(s)(R³)_(t)  (V) where M¹ is an alkali metal, an alkalineearth metal or a metal of group 13 of the Periodic Table, R¹ ishydrogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl, halo-C₁-C₁₀-alkyl,halo-C₆-C₁₅-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, C₁-C₁₀-alkoxy ,halo-C₇-C₄₀-alkylaryl, halo-C₇-C₄₀-arylalkyl or halo-C₁-C₁₀-alkoxy, R²and R³ are each hydrogen, C₁-C₁₀-alkyl, C₆-C₁₅-aryl, halo-C₁-C₁₀-alkyl,halo-C₆-C₁₅-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, C₁-C₁₀-alkoxy orhalo-C₇-C₄₀-alkylaryl, halo-C₇-C₄₀-arylalkyl or halo-C₁-C₁₀-alkoxy, r isan integer from 1 to 3 and s and t are integers from 0 to 2, where thesum r+s+t corresponds to the valence of M¹, and C) at least onecation-forming compound into contact with one another, wherein theorganic transition metal compound A) is firstly combined with themixture of the organo metallic compounds B).
 2. A process for preparinga catalyst for olefin polymerization as claimed in claimi, wherein D) atleast one support is used as further component.
 3. A process forpreparing a catalyst for olefin polymerization as claimed in claim 2,wherein E) at least one Lewis base is used as further component.
 4. Aprocess for preparing a catalyst for olefin polymerization as claimed inclaim 3, wherein the cation-forming compound is a strong uncharged Lewisacid, an ionic compound having a Lewis-acid cation, an ionic compoundcontaining a Brönsted acid as cation or an aluminoxane or a modifiedaluminoxane in which at least some of the hydrocarbon radicals arereplaced by alkoxy, aryloxy, siloxy or amide groups.
 5. A process forpreparing a catalyst for olefin polymerization as claimed in claim 4,wherein the at least one cation-forming compound is obtained during thepreparation of the catalyst by reacting a compound having at least onefunctional group containing active hydrogen with an organometalliccompound.
 6. A process for preparing a catalyst for olefinpolymerization as claimed in claim 1, wherein B) at least one Lewis baseis used as further component.
 7. A process for preparing a catalyst forolefin polymerization as claimed in claim 1, wherein the cation-formingcompound is a strong uncharged Lewis acid, an ionic compound having aLewis-acid cation, an ionic compound containing a Brönsted acid ascation, an aluminoxane or a modified aluminoxane in which at least someof the hydrocarbon radicals are replaced by alkoxy, aryloxy, siloxy oramide groups.
 8. A process for preparing a catalyst for olefinpolymerization as claimed in claim 1, wherein the at least onecation-forming compound is obtained during the preparation of thecatalyst by reacting a compound having at least one functional groupcontaining active hydrogen with an organometallic compound.
 9. A processfor preparing a catalyst for olefin polymerization as claimed in claim8, wherein the compound having at least one functional group containingactive hydrogen is a hydroxyl-containing compound.
 10. A process forpreparing a catalyst for olefin polymerization as claimed in claim 9,wherein the hydroxyl groups are bound to an element of main group 13, 14or 15 of the Periodic Table.